Azeotrope-like compositions of 1,1,2,3,3-pentafluoropropene

ABSTRACT

The invention pertains to azeotrope-like compositions of 1,1,2,3,3-pentafluoropropene (HFC-1225yc) and any one of 1,1,1,2-tetrafluoropropene (HFC-1234yf) or the Z-isomer of 1,1,1,2,3-pentafluoropropene (HFC-1225yeZ), and uses thereof, including use in refrigerant compositions, refrigeration systems, blowing agent compositions, and aerosol propellants.

BACKGROUND OF THE INVENTION

1. Field of Invention

The invention pertains to azeotrope-like compositions of1,1,2,3,3-pentafluoropropene (HFO-1225yc) and any one of1,1,1,2-tetrafluoropropene (HFO-1234yf) or the Z-isomer of1,1,1,2,3-pentafluoropropene (HFO-1225yeZ), and uses thereof.

2. Description of the Related Art

Fluorocarbon based fluids have found widespread use in industry in anumber of applications, including as refrigerants, aerosol propellants,blowing agents, heat transfer media, and gaseous dielectrics. Because ofthe suspected environmental problems associated with the use of some ofthese fluids, including the relatively high global warming potentialsassociated therewith, it is desirable to use fluids having low or evenzero ozone depletion potential. Thus, the use of fluids that do notcontain chlorofluorocarbons (“CFCs”) or hydrochlorofluorocarbons(“HCFCs”) is desirable. Compounds having a low ozone depletion potentialinclude hydrofluorocarbons (“HFCs”), especially hydrofluoroolefins(“HFO's”). Compounds having a low global warming potential are alsodesirable. In this regard, the use of alkenes is also desirable due totheir short atmospheric lifetime which results in a relatively lowglobal warming potential. Additionally, the use of single componentfluids or azeotropic mixtures, which do not fractionate on boiling andevaporation, is desirable. However, the identification of new,environmentally safe, non-fractionating mixtures is complicated due tothe fact that azeotrope formation is not readily predictable.

The industry is continually seeking new fluorocarbon based mixtures thatoffer alternatives, and are considered environmentally safer substitutesfor CFCs and HCFCs. Of particular interest are mixtures containinghydrofluorocarbons, fluoroolefins and other fluorinated compounds, whichhave a low ozone depletion potentials and low global warming potential.Such mixtures are the subject of this invention.

U.S. Pat. No. 6,858,571 describes azeotrope-like compositions comprisingpentafluoropropene (HFO-1225) and a fluid selected from the groupconsisting of 3,3,3-trifluoropropene (“HFO-1243zf”), 11-difluoroethane(“HFC-152a”), trans-1,3,3,3-tetrafluoropropene (“HFO-1234ze”), andcombinations of two or more thereof. However, U.S. Pat. No. 6,858,571does not show azeotrope-like composition comprising HFO-1225yc witheither HFO-1234yf or HFO-1225yeZ. The invention concerns compositionsthat help to satisfy the continuing need for alternatives to CFCs andHCFCs. The compositions of the invention exhibit relatively low globalwarming potentials (“GWP”). Accordingly, applicants have recognized thatsuch compositions can be used to great advantage in a number ofapplications, including as replacements for CFCs, HCFC's, and HFCs inrefrigerant, aerosol, blowing agents, and other applications.

DETAILED DESCRIPTION OF THE INVENTION

Accordingly, the present invention provides azeotrope-like compositionscomprising 1,1,2,3,3-pentafluoropropene (HFO-1225yc) and any one of1,1,1,2-tetrafluoropropene (HFO-1234yf) or the Z-isomer of1,1,1,2,3-pentafluoropropene (HFO-1225yeZ). One embodiment of theinvention provides an azeotrope-like composition comprising1,1,2,3,3-pentafluoropropene and, 1,1,1,2-tetrafluoropropene. Anotherembodiment of the invention provides an azeotrope-like compositioncomprising 1,1,2,3,3-pentafluoropropene and the Z-isomer of1,1,1,2,3-pentafluoropropene. The azeotrope-like compositions of thepresent invention exhibits properties that make that make themadvantageous for use as, or in, a refrigerant, an aerosol, and blowingagent compositions.

The invention further provides a method for modifying a refrigerationapparatus which refrigeration apparatus comprises a refrigerant, whichrefrigerant comprises a combination of a chlorofluorocarbon or ahydrochlorofluorocarbon and a mineral oil, comprising removing at leasta portion of the chlorofluorocarbon or hydrochlorofluorocarbon from therefrigerant and leaving a residue comprising the mineral oil, and addingto said residue an azeotrope-like composition comprising1,1,2,3,3-pentafluoropropene and any one of 1,1,1,2-tetrafluoropropeneor the Z-isomer of 1,1,1,2,3-pentafluoropropene.

As used herein, the term “azeotrope-like” is intended in its broad senseto include both compositions that are strictly azeotropic andcompositions that behave like azeotropic mixtures. From fundamentalprinciples, the thermodynamic state of a fluid is defined by pressure,temperature, liquid composition, and vapor composition. An azeotropicmixture is a system of two or more components in which the liquidcomposition and vapor composition are equal at the stated pressure andtemperature. In practice, this means that the components of anazeotropic mixture are constant boiling and cannot be separated during aphase change. The azeotrope-like compositions of the invention mayinclude additional components that do not form new azeotrope-likesystems, or additional components that are not in the first distillationcut. The first distillation cut is the first cut taken after thedistillation column displays steady state operation under total refluxconditions. One way to determine whether the addition of a componentforms a new azeotrope-like system so as to be outside of this inventionis to distill a sample of the composition with the component underconditions that would be expected to separate a non-azeotropic mixtureinto its separate components. If the mixture containing the additionalcomponent is non-azeotrope-like, the additional component willfractionate from the azeotrope-like components. If the mixture isazeotrope-like, some finite amount of a first distillation cut will beobtained that contains all of the mixture components that is constantboiling or behaves as a single substance. It follows from this thatanother characteristic of azeotrope-like compositions is that there is arange of compositions containing the same components in varyingproportions that are azeotrope-like or constant boiling. All suchcompositions are intended to be covered by the terms “azeotrope-like”and “constant boiling”. As an example, it is well known that atdiffering pressures, the composition of a given azeotrope will vary atleast slightly, as does the boiling point of the composition. Thus, anazeotrope of A and B represents a unique type of relationship, but witha variable composition depending on temperature and/or pressure. Itfollows that, for azeotrope-like compositions, there is a range ofcompositions containing the same components in varying proportions thatare azeotrope-like. All such compositions are intended to be covered bythe term azeotrope-like as used herein. It is well recognized in the artthat it is not possible to predict the formation of azeotropes. (See,for example, U.S. Pat. No. 5,648,017 (column 3, lines 64-65) and U.S.Pat. No. 5,182,040 (column 3, lines 62-63), both of which areincorporated herein by reference). It has been unexpectedly discoveredthat 1,1,2,3,3-pentafluoropropene (HFO-1225yc) and any one of1,1,1,2-tetrafluoropropene (HFO-1234yf) or the Z-isomer of1,1,1,2,3-pentafluoropropene (HFO-1225yeZ), form azeotrope-likecompositions.

According to certain preferred embodiments, the azeotrope-likecompositions of the present invention comprise, and preferably consistessentially of, effective amounts of 1,1,2,3,3-pentafluoropropene(HFO-1225yc) and any one of 1,1,1,2-tetrafluoropropene (HFO-1234yf) orthe Z-isomer of 1,1,1,2,3-pentafluoropropene (HFO-1225yeZ). The term“effective amounts” as used herein refers to the amount of eachcomponent which upon combination with the other component, results inthe formation of an azeotrope-like composition of the present invention.

The azeotrope-like compositions of the present invention can be producedby combining effective amounts of 1,1,2,3,3-pentafluoropropene(HFO-1225yc) and any one of 1,1,1,2-tetrafluoropropene (HFO-1234yf) orthe Z-isomer of 1,1,1,2,3-pentafluoropropene (HFO-1225yeZ). Any of awide variety of methods known in the art for combining two or morecomponents to form a composition can be adapted for use in the presentmethods to produce an azeotrope-like composition. For example, the1,1,2,3,3-pentafluoropropene (HFO-1225yc) and any one of1,1,1,2-tetrafluoropropene (HFO-1234yf) or the Z-isomer of1,1,1,2,3-pentafluoropropene (HFO-1225yeZ), can be mixed, blended, orotherwise contacted by hand and/or by machine, as part of a batch orcontinuous reaction and/or process, or via combinations of two or moresuch steps. In light of the disclosure herein, those skilled in the artwill be readily able to prepare azeotrope-like compositions according tothe present invention without undue experimentation.

The 1,1,2,3,3-pentafluoropropene (HFO-1225yc) and any one of1,1,1,2-tetrafluoropropene (HFO-1234yf) or the Z-isomer of1,1,1,2,3-pentafluoropropene (HFO-1225yeZ) are present in amountseffective to produce an azeotrope-like composition. In one embodimentthe 1,1,2,3,3-pentafluoropropene (HFO-1225yc) is present in theazeotrope-like composition in an amount of from greater than zero toabout 25 weight percent, preferably from greater than zero to about 20weight percent, and more preferably from about 2 to about 15 weightpercent. In one embodiment the 1,1,1,2-tetrafluoropropene (HFO-1234yf)or the Z-isomer of 1,1,1,2,3-pentafluoropropene (HFO-1225yeZ) is presentin the azeotrope-like composition in an amount of from about 75 to lessthan 100 weight percent, preferably from about 80 to less than 100weight percent, and more preferably from about 85 to about 98 weightpercent.

The azeotrope-like composition of 1,1,2,3,3-pentafluoropropene and1,1,1,2-tetrafluoropropene has a boiling point at about 14.5 psia offrom about −29° C. to about −27.5° C.; preferably from about −29° C. toabout −28° C.

The azeotrope-like composition of 1,1,2,3,3-pentafluoropropene and theZ-isomer of 1,1,1,2,3-pentafluoropropene has a boiling point at about14.5 psia of from about −19.2° C. to about −188.9, preferably from about−19.2° C. to about −19° C.

The present azeotrope-like compositions have utility in a wide range ofapplications. For example, as a blowing agent, as part of a sprayablecomposition such as an aerosol composition, as cleaning composition, ora refrigerant composition.

Yet another embodiment of the present invention relates to a blowingagent comprising one or more azeotrope-like compositions of theinvention. One embodiment of the present invention relates to methods offorming thermoset foams, and preferably polyurethane andpolyisocyanurate foams. The methods generally comprise providing ablowing agent composition of the present inventions, directly orindirectly adding the blowing agent composition to a foamablecomposition, and reacting the foamable composition under the conditionseffective to form a foam or cellular structure, as is well known in theart. These comprise a foamable composition comprising the azeotrope-likecomposition above and at least one thermoset foam component. Forexample, the thermoset foam component may comprise a composition capableof forming a polyurethane foam, a polyisocyanurate foam or a phenolicfoam. It is possible to produce thermoplastic foams using thecompositions of the invention. These foams may be open cell or closedcell. Any of the methods well known in the art, such as those describedin “Polyurethanes Chemistry and Technology,” Volumes I and II, Saundersand Frisch, 1962, John Wiley and Sons, New York, N.Y., which isincorporated herein by reference, may be used or adapted for use inaccordance with the foam embodiments of the present invention.

In general, polyurethane or polyisocyanurate foams are prepared bycombining an isocyanate, the polyol premix composition, and othermaterials such as optional flame retardants, colorants, or otheradditives. These foams can be rigid, flexible, or semi-rigid, and canhave a closed cell structure, an open cell structure or a mixture ofopen and closed cells. In general, such preferred methods comprisepreparing polyurethane or polyisocyanurate foams by combining anisocyanate, a polyol or mixture of polyols, a blowing agent or mixtureof blowing agents comprising one or more of the present compositions,and other materials such as catalysts, surfactants, and optionally,flame retardants, colorants, or other additives.

It is convenient in many applications to provide the components forpolyurethane or polyisocyanurate foams in pre-blended formulations. Mosttypically, the foam formulation is pre-blended into two components. Theisocyanate and optionally certain surfactants and blowing agentscomprise the first component, commonly referred to as the “A” component.The polyol or polyol mixture, a surfactant including siliconesurfactants, catalysts including amine catalysts, blowing agents, flameretardant, and other isocyanate reactive components comprise the secondcomponent, commonly referred to as the “B” component. The blowing agentcomprises the azeotrope-like composition of this invention andoptionally a hydrocarbon, halogenated hydrocarbon, CO₂ generatingmaterial, or combinations thereof. Preferably the halogenatedhydrocarbon comprises a chlorofluorocarbon, hydrochlorofluorocarbon,hydrofluorocarbon, or combinations thereof. The blowing agent componentis usually present in the polyol premix composition in an amount of fromabout 1 wt. % to about 30 wt. %, by weight of the polyol premixcomposition. The polyol component, can be any polyol which reacts in aknown fashion with an isocyanate in preparing a polyurethane orpolyisocyanurate foam. Useful polyols comprise one or more of a sucrosecontaining polyol; phenol, a phenol formaldehyde containing polyol; aglucose containing polyol; a sorbitol containing polyol; amethylglucoside containing polyol; an aromatic polyester polyol;glycerol; ethylene glycol; diethylene glycol; propylene glycol; graftcopolymers of polyether polyols with a vinyl polymer; a copolymer of apolyether polyol with a polyurea; or combinations thereof. The polyolcomponent is usually present in the polyol premix composition in anamount of from about 60 wt. % to about 95 wt. %, by weight of the polyolpremix composition. The polyol premix composition next contains asurfactant component which silicone surfactant and optionally anadditional non-silicone surfactant. The surfactant is usually present inthe polyol premix composition in an mount of from about 0.5 wt. % toabout 5.0 wt. % by weight of the polyol premix composition. The polyolpremix composition next contains a catalyst which is preferably anamine. Tertiary amines are preferred. Preferred amines include:N,N-dimethylcyclohexylamine, dimethlyethanolamine,N,N,N′,N′,N″,N″-pentamethyldiethylenetriamine, 1,4-diaza-bicyclo[2.2.2]octane (DABCO), and triethylamine. The catalyst is usuallypresent in the polyol premix composition in an amount of from about 0.1wt. % to about 3.5 wt. % by weight of the polyol premix composition.

A foamable composition suitable for forming a polyurethane orpolyisocyanurate foam may be formed by reacting an organicpolyisocyanate and the polyol premix composition described above. Anyorganic polyisocyanate can be employed in polyurethane orpolyisocyanurate foam synthesis inclusive of aliphatic and aromaticpolyisocyanates. Suitable organic polyisocyanates include aliphatic,cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanateswhich are well known in the field of polyurethane chemistry. These aredescribed in, for example, U.S. Pat. Nos. 4,868,224; 3,401,190;3,454,606; 3,277,138; 3,492,330; 3,001,973; 3,394,164; 3,124.605; and3,201,372. Preferred as a class are the aromatic polyisocyanates.Representative organic polyisocyanates correspond to the formula:

R(NCO)z

wherein R is a polyvalent organic radical which is either aliphatic,aralkyl, aromatic or mixtures thereof, and z is an integer whichcorresponds to the valence of R and is at least two.

Accordingly, polyurethane or polyisocyanurate foams are readily preparedby bringing together the A and B side components either by hand mix forsmall preparations and, preferably, machine mix techniques to formblocks, slabs, laminates, pour-in-place panels and other items, sprayapplied foams, froths, and the like. Optionally, other ingredients suchas fire retardants, colorants, auxiliary blowing agents, and even otherpolyols can be added as a third stream to the mix head or reaction site.Most preferably, however, they are all incorporated into one B-componentas described above. Conventional flame retardants can also beincorporated, preferably in amount of not more than about 20 percent byweight of the reactants.

In addition to the previously described ingredients, other ingredientssuch as, dyes, fillers, pigments and the like can be included in thepreparation of the foams. Dispersing agents and cell stabilizers can beincorporated into the present blends. Conventional fillers for useherein include, for example, aluminum silicate, calcium silicate,magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate,glass fibers, carbon black and silica. The filler, if used, is normallypresent in an amount by weight ranging from about 5 parts to 100 partsper 100 parts of polyol. A pigment which can be used herein can be anyconventional pigment such as titanium dioxide, zinc oxide, iron oxide,antimony oxide, chrome green, chrome yellow, iron blue siennas,molybdate oranges and organic pigments such as para reds, benzidineyellow, toluidine red, toners and phthalocyanines. The polyurethane orpolyisocyanurate foams produced can vary in density from about 0.5pounds per cubic foot to about 60 pounds per cubic foot, preferably fromabout 1.0 to 20.0 pounds per cubic foot, and most preferably from about1.5 to 6.0 pounds per cubic foot. The density obtained is a function ofhow much of the blowing agent or blowing agent mixture disclosed in thisinvention plus the amount of auxiliary blowing agent, such as water orother co-blowing agents is present in the A and/or B components, oralternatively added at the time the foam is prepared. These foams can berigid, flexible, or semi-rigid foams, and can have a closed cellstructure, an open cell structure or a mixture of open and closed cells.These foams are used in a variety of well known applications, includingbut not limited to thermal insulation, cushioning, flotation, packaging,adhesives, void filling, crafts and decorative, and shock absorption.

The invention also contemplates forming a thermoplastic form. Forexample, conventional polystyrene and polyethylene formulations may becombined with the azeotrope-like composition in a conventional manner toproduce thermoplastic foams. Examples of thermoplastic foam componentsinclude polyolefins, such as for example polystyrene. Other examples ofthermoplastic resins include polyethylene, ethylene copolymers,polypropylene, and polyethyleneterephthalate. In certain embodiments,the thermoplastic foamable composition is an extrudable composition. Itis also generally recognized that the thermoplastic foamable compositionmay include adjuvants such as nucleating agents, flame or fire retardantmaterials, cell modifiers, cell pressure modifiers, and the like.

With respect to thermoplastic foams, the preferred methods generallycomprise introducing a blowing agent in accordance with the presentinvention into a thermoplastic material, and then subjecting thethermoplastic material to conditions effective to cause foaming. Forexample, the step of introducing the blowing agent into thethermoplastic material may comprise introducing the blowing agent into ascrew extruder containing a thermoplastic polymer, and the step ofcausing foam may comprise lowering the pressure on the thermoplasticmaterial and thereby causing expansion of the blowing agent andcontributing to the foaming of the material. Suitable thermoplasticpolymers non-exclusively include polystyrene, polyethylene,polypropylene, polyethylene terephthalate, and combinations of these. Itwill be generally appreciated by those skilled in the art, especially inview of the disclosure herein, that the order and manner in which theblowing agent of the present invention is formed and/or added to thefoamable composition does not generally affect the operability of thepresent invention thermoset or thermoplastic foams. It is contemplatedalso that in certain embodiments it may be desirable to utilize thepresent compositions when in the supercritical or near supercriticalstate as a blowing agent.

The azeotrope-like compositions of this invention may also be used asrefrigerant compositions. The refrigerant compositions of the presentinvention may be used in any of a wide variety of refrigeration systemsincluding air-conditioning, refrigeration, heat-pump systems, and thelike. In certain preferred embodiments, the compositions of the presentinvention are used in refrigeration systems originally designed for usewith an HFC-refrigerant, such as, for example, HFC-134a. The preferredcompositions of the present invention tend to exhibit many of thedesirable characteristics of HFC-134a and other HFC-refrigerants,including non-flammability, and a GWP that is as low, or lower than thatof conventional HFC-refrigerants. In addition, the relatively constantboiling nature of the compositions of the present invention makes themeven more desirable than certain conventional HFCs for use asrefrigerants in many applications.

In certain other preferred embodiments, the present compositions areused in refrigeration systems originally designed for use with aCFC-refrigerant. Preferred refrigeration compositions of the presentinvention may be used in refrigeration systems containing a lubricantused conventionally with CFC-refrigerants, such as mineral oils,silicone oils, and the like, or may be used with other lubricantstraditionally used with HFC refrigerants. In certain embodiments, thecompositions of the present invention may be used to retrofitrefrigeration systems containing HFC, HCFC, and/or CFC-refrigerants andlubricants used conventionally therewith. Preferably, the presentmethods involve recharging a refrigerant system that contains arefrigerant to be replaced and a lubricant comprising the steps of (a)removing at least a portion of the refrigerant to be replaced from therefrigeration system while retaining a substantial portion of thelubricant in said system; and (b) introducing to the system acomposition of the present invention. As used herein, the term“substantial portion” refers generally to a quantity of lubricant whichis at least about 50% by weight of the quantity of lubricant containedin the refrigeration system prior to removal of the chlorine-containingrefrigerant. Preferably, the substantial portion of lubricant in thesystem according to the present invention is a quantity of at leastabout 60% of the lubricant contained originally in the refrigerationsystem, and more preferably a quantity of at least about 70%. As usedherein the term “refrigeration system” refers generally to any system orapparatus, or any part or portion of such a system or apparatus, whichemploys a refrigerant to provide cooling. Such refrigeration systemsinclude, for example, air conditioners, electric refrigerators,chillers, transport refrigeration systems, commercial refrigerationsystems and the like.

Any of a wide range of known methods can be used to remove refrigerantsto be replaced from a refrigeration system while removing less than amajor portion of the lubricant contained in the system. For example,because refrigerants are quite volatile relative to traditionalhydrocarbon-based lubricants where the boiling points of refrigerantsare generally less than 10° C. whereas the boiling points of mineraloils are generally more than 200° C. In embodiments wherein thelubricant is a hydrocarbon-based lubricant, the removal step may readilybe performed by pumping chlorine-containing refrigerants in the gaseousstate out of a refrigeration system containing liquid state lubricants.Such removal can be achieved in any of a number of ways known in theart, including, the use of a refrigerant recovery system, such as therecovery system manufactured by Robinair of Ohio. Alternatively, acooled, evacuated refrigerant container can be attached to the lowpressure side of a refrigeration system such that the gaseousrefrigerant is drawn into the evacuated container and removed. Moreover,a compressor may be attached to a refrigeration system to pump therefrigerant from the system to an evacuated container. In light of theabove disclosure, those of ordinary skill in the art will be readilyable to remove chlorine-containing lubricants from refrigeration systemsand to provide a refrigeration system having therein a hydrocarbon-basedlubricant and substantially no chlorine-containing refrigerant accordingto the present invention.

Any of a wide range of methods for introducing the present refrigerantcompositions to a refrigeration system can be used in the presentinvention. For example, one method comprises attaching a refrigerantcontainer to the low-pressure side of a refrigeration system and turningon the refrigeration system compressor to pull the refrigerant into thesystem. In such embodiments, the refrigerant container may be placed ona scale such that the amount of refrigerant composition entering thesystem can be monitored. When a desired amount of refrigerantcomposition has been introduced into the system, charging is stopped.Alternatively, a wide range of charging tools, known to those of skillin the art, is commercially available. Accordingly, in light of theabove disclosure, those of skill in the art will be readily able tointroduce the refrigerant compositions of the present invention intorefrigeration systems according to the present invention without undueexperimentation.

According to certain other embodiments, the present invention providesrefrigeration systems comprising a refrigerant of the present inventionand methods of producing heating or cooling by condensing and/orevaporating a composition of the present invention. In certain preferredembodiments, the methods for cooling an article according to the presentinvention comprise condensing a refrigerant composition comprising anazeotrope-like composition of the present invention and thereafterevaporating said refrigerant composition in the vicinity of the articleto be cooled. Certain preferred methods for heating an article comprisecondensing a refrigerant composition comprising an azeotrope-likecomposition of the present invention in the vicinity of the article tobe heated and thereafter evaporating said refrigerant composition. Inlight of the disclosure herein, those of skill in the art will bereadily able to heat and cool articles according to the presentinventions without undue experimentation.

In another embodiment, the azeotrope-like compositions of this inventionmay be used as propellants in sprayable compositions, either alone or incombination with known propellants. The propellant compositioncomprises, more preferably consists essentially of, and, even morepreferably, consists of the azeotrope-like compositions of theinvention. The active ingredient to be sprayed together with inertingredients, solvents, and other materials may also be present in thesprayable mixture. Preferably, the sprayable composition is an aerosol.Suitable active materials to be sprayed include, without limitation,cosmetic materials such as deodorants, perfumes, hair sprays, cleansers,defluxing agents, and polishing agents as well as medicinal materialssuch as anti-asthma and anti-halitosis medications. Other uses of thepresent azeotrope-like compositions include use as solvents, cleaningagents, and the like. Those skilled in the art will be readily able toadapt the present compositions for use in such applications withoutundue experimentation.

EXAMPLES

The following non-limiting examples serve to illustrate the invention.

Example 1

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which is further equipped with a Quartz Thermometer is used. About9.54 g HFO-1234yf is charged to the ebulliometer and then HFO-1225yc isadded in small, measured increments. Temperature depression is observedwhen HFO-1225yc is added to HFO-1234yf, indicating a binary minimumboiling azeotrope is formed. From greater than about 0 to about 21weight percent HFO-1225yc, the boiling point of the composition staysbelow or around the boiling point of HFO-1234yf. The boiling temperatureof HFO-1225yc is about 2° C. at 14.71 psia. The binary mixtures shown inTable 1 were studied and the boiling point of the compositions did notgo above the boiling point of HFO-1234 yf. The compositions exhibitazeotrope and/or azeotrope-like properties over this range.

TABLE 1 HFO-1234yf/HFO-1225yc compositions at 14.7 psia Wt. % Wt. % T (°C.) HFO-1234yf HFO-1225yc −27.860 100.00 0.00 −28.435 99.58 0.42 −28.69198.55 1.45 −28.873 97.15 2.85 −28.871 94.55 5.45 −28.763 92.62 7.38−28.649 91.38 8.62 −28.482 89.33 10.67 −28.349 87.44 12.56 −28.090 81.7518.25 −27.742 78.91 21.09 −27.529 76.75 23.25 −27.182 73.44 26.56−26.966 68.49 31.51 −26.820 61.95 38.05 −26.572 59.74 40.26

Example 2 (Comparative)

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which is further equipped with a Quartz Thermometer is used. About17.92 g 1,3,3,3-tetrafluoropropene (trans-HFO-1234ze) is charged to theebulliometer and then HFO-1225yc is added in small, measured increments.Temperature depression is observed when HFO-1225yc is added toTrans-1234ze, indicating a binary minimum boiling azeotrope is formed.From greater than about 0 to about 7 weight percent HFO-1225yc, theboiling point of the composition stays below or around the boiling pointof Trans-1234ze. The binary mixtures shown in Table 2 were studied andthe boiling point of the compositions did not go above the boiling pointof Trans-1234ze. The compositions exhibit azeotrope and/orazeotrope-like properties over this range.

TABLE 2 Trans-1234ze/1225yc compositions at 14.5 psia Wt. % Wt. % T (°C.) Trans-HFO-1234ze HFO-1225yc −18.353 100.00 0.00 −18.420 99.01 0.99−18.461 96.66 3.34 −18.458 95.43 4.57 −18.315 92.81 7.19

Example 3

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which is further equipped with a Quartz Thermometer is used. About19.57 g HFO-1225yeZ is charged to the ebulliometer and then HFO-1225ycis added in small, measured increments. Temperature depression isobserved when HFO-1225yc is added to HFO-1225yeZ, indicating a binaryminimum boiling azeotrope is formed. From greater than about 0 to about5 weight percent HFO-1225yc, the boiling point of the composition staysbelow or around the boiling point of HFO-1225yeZ. The binary mixturesshown in Table 3 were studied and the boiling point of the compositionsdid not go above the boiling point of HFO-1225yeZ. The compositionsexhibit azeotrope and/or azeotrope-like properties over this range.

TABLE 3 HFO-1225yeZ/HFO-1225yc compositions at 14.5 psia Wt. % Wt. % T(° C.) HFO-225yeZ HFO-1225yc −18.854 100.00 0.00 −18.909 98.89 1.11−18.989 97.56 2.44 −19.154 96.07 3.93 −19.124 95.37 4.63

Example 4 (Comparative)

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which is further equipped with a Quartz Thermometer is used. About15.11 g 3,3,3-trifluoropropene is charged to the ebulliometer and thenHFO-1225yc is added in small, measured increments. Temperaturedepression is observed when HFO-1225yc is added to3,3,3-trifluoropropene, indicating a binary minimum boiling azeotrope isformed. From greater than about 0 to about 10 weight percent HFO-1225yc,the boiling point of the composition stays below or around the boilingpoint of 3,3,3-trifluoropropene. The binary mixtures shown in Table 4were studied and the boiling point of the compositions did not go abovethe boiling point of 3,3,3-trifluoropropene. The compositions exhibitazeotrope and/or azeotrope-like properties over this range.

TABLE 4 3,3,3-trifluoropropene/HFO-1225yc compositions at 14.5 psia Wt.% Wt. % T (° C.) 3,3,3-trifluoropropene HFO-1225yc −24.601 100.00 0.00−24.607 99.87 0.13 −24.877 95.51 4.49 −24.864 93.50 6.50 −24.646 89.2010.80

While the present invention has been particularly shown and describedwith reference to preferred embodiments, it will be readily appreciatedby those of ordinary skill in the art that various changes andmodifications may be made without departing from the spirit and scope ofthe invention. It is intended that the claims be interpreted to coverthe disclosed embodiment, those alternatives which have been discussedabove and all equivalents thereto.

1. An azeotrope-like composition comprising 1,1,2,3,3-pentafluoropropeneand any one of 1,1,1,2-tetrafluoropropene or the Z-isomer of1,1,1,2,3-pentafluoropropene.
 2. The azeotrope-like composition of claim1 comprising 1,1,2,3,3-pentafluoropropene and1,1,1,2-tetrafluoropropene.
 3. The azeotrope-like composition of claim 1comprising 1,1,2,3,3-pentafluoropropene and the Z-isomer of1,1,1,2,3-pentafluoropropene.
 4. The azeotrope-like composition of claim1 which comprises from greater than zero to about 25 weight percent1,1,2,3,3-pentafluoropropene and from about 75 to less than 100 weightpercent of 1,1,1,2-tetrafluoropropene or the Z-isomer of1,1,1,2,3-pentafluoropropene.
 5. The azeotrope-like composition of claim1 which comprises from greater than zero to about 20 weight percent1,1,2,3,3-pentafluoropropene and from about 80 to less than 100 weightpercent of 1,1,1,2-tetrafluoropropene or the Z-isomer of1,1,1,2,3-pentafluoropropene.
 6. The azeotrope-like composition of claim1 which comprises from about 2 to about 15 weight percent1,1,2,3,3-pentafluoropropene and from about 85 to about 98 weightpercent of 1,1,1,2-tetrafluoropropene or the Z-isomer of1,1,1,2,3-pentafluoropropene.
 7. The azeotrope-like composition of claim2 having a boiling point of from about −29° C. to about −27.5° C. at apressure of about 14.5 psia.
 8. The azeotrope-like composition of claim2 having a boiling point of from about −29° C. to about −28° C. at apressure of about 14.5 psia.
 9. The azeotrope-like composition of claim3 having a boiling point of from about −19.2° C. to about −18.9° C. at apressure of about 14.5 psia.
 10. The azeotrope-like composition of claim3 having a boiling point of from about −19.2° C. to about −19° C. at apressure of about 14.5 psia.
 11. A sprayable composition comprising amaterial to be sprayed and a propellant comprising the azeotrope-likecomposition of claim
 1. 12. A refrigerant composition comprising theazeotrope-like composition of claim
 1. 13. A refrigeration systemcomprising the refrigerant of claim
 12. 14. A method for cooling anarticle which comprises condensing a refrigerant composition of claim 12and thereafter evaporating said refrigerant composition in the vicinityof the article to be cooled.
 15. A method for heating an article whichcomprises condensing a refrigerant composition of claim 12 in thevicinity of the article to be heated and thereafter evaporating saidrefrigerant composition.
 16. A method of recharging a refrigerant systemthat contains a refrigerant to be replaced and a lubricant comprisingthe steps of: (a) removing at least a portion of the refrigerant to bereplaced from the refrigeration system while retaining a substantialportion of the lubricant in said system; and (b) introducing to thesystem a refrigerant composition of claim
 12. 17. A blowing agentcomprising the azeotrope-like composition of claim
 1. 18. A foamablecomposition comprising the azeotrope-like composition of claim 1 and atleast one thermoset foam component.
 19. The foamable composition ofclaim 18, wherein said at least one thermoset component comprises acomposition capable of forming a polyurethane foam.
 20. The foamablecomposition of claim 18 wherein said at least one thermoset componentcomprises a composition capable of forming a polyisocyanurate foam. 21.The foamable composition of claim 18 wherein said at least one thermosetcomponent comprises a composition capable of forming a phenolic foam.22. A polyol premix composition which comprises a combination of ablowing agent, a polyol, a surfactant, and an amine catalyst, whereinthe blowing agent comprises the azeotrope-like composition of claim 1and optionally a hydrocarbon, halogenated hydrocarbon, CO₂ generatingmaterial, or combinations thereof.
 23. The polyol premix composition ofclaim 22 wherein the halogenated hydrocarbon comprises achlorofluorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, orcombinations thereof.
 24. A foamable composition comprising a mixture ofan organic polyisocyanate and the polyol premix composition of claim 22.25. A foamable composition comprising the azeotrope-like composition ofclaim 1 and at least one thermoplastic foam component.
 26. The foamablecomposition of claim 25, wherein said at least one thermoplastic foamcomponent comprises a thermoplastic polymer.
 27. The foamablecomposition of claim 26 wherein said thermoplastic polymer comprises apolystyrene, polyethylene, polypropylene, polyethyleneterephthalate, andcombinations of these.
 28. A method for modifying a refrigerationapparatus which refrigeration apparatus comprises a refrigerant, whichrefrigerant comprises a combination of a chlorofluorocarbon or ahydrochlorofluorocarbon and a mineral oil, comprising removing at leasta portion of the chlorofluorocarbon or hydrochlorofluorocarbon from therefrigerant and leaving a residue comprising the mineral oil, and addingto said residue an azeotrope-like composition comprising1,1,2,3,3-pentafluoropropene and any one of 1,1,1,2-tetrafluoropropeneor the Z-isomer of 1,1,1,2,3-pentafluoropropene.